Emulsifiers

ABSTRACT

An emulsifier for use in making PIT or microemulsions is comprised of (a) from 45 to 60% by weight of a partial glyceride, (b) from 5 to 25% by weight of an alcohol polyglycol ether, (C) from 5 to 15% by weight fatty alcohol, and (d) from 0 to 15% by weight of a wax ester wherein the monoglyceride content of the partial glyceride is less than 50% by weight and wherein the monoglyceride is comprised of palmitic and stearic acid residues in a ratio by weight of from 40:60 to 60:40. Emulsions containing these emulsifiers neither gel nor crystallize in storage.

This invention relates generally to cosmetics and, more particularly, tonew emulsifiers distinguished by improved phase behaviour.

Emulsions distinguished by a particularly elegant appearance and dropletfineness are acquiring increasing significance in the field ofcosmetics. These PIT emulsions or microemulsions with average dropletsizes of 500 nm and smaller are produced by known processes whichinvolve the use of special emulsifiers. The most important productsinclude mixtures of partial glycerides, fatty alcohol polyglycol ethersand fatty alcohols. Unfortunately, these emulsifiers are unsatisfactorybecause the PIT emulsions or microemulsions produced with themoccasionally tend to gel or crystallize in storage, particularly undertemperature stress.

Accordingly, the problem addressed by the present invention was toprovide new emulsifiers based on partial glycerides, alcohol polyglycolethers and fatty alcohols which would be free from the disadvantagesmentioned above.

DESCRIPTION OF THE INVENTION

The present invention relates to emulsifiers containing

-   (a) partial glycerides,-   (b) alcohol polyglycol ethers and-   (c) fatty alcohols,    which are distinguished by the fact that the partial glycerides have    a percentage monoglyceride content of less than 50% by weight and    preferably in the range from 30 to 45% by weight.

It has surprisingly been found that, in contrast to the known products,the new emulsifiers allow the production of PIT emulsions ormicroemulsions which neither gel nor crystallize, even in storage. Thiseffect can be further improved through the choice and ratio of the acylgroups in the partial glyceride component.

Partial Glycerides

Partial glycerides, i.e. monoglycerides, diglycerides and technicalmixtures thereof, which form component (a) can also contain smallquantities of triglycerides from their production. The partialglycerides preferably correspond to formula (I):

where R¹CO is a linear or branched, saturated and/or unsaturated acylgroup containing 6 to 24 and preferably 12 to 18 carbon atoms, R² and R³independently of one another have the same meaning as R¹CO or representOH and the sum (m+n+p) is 0 or a number of 1 to 100 and preferably 5 to25, with the proviso that at least one of the two substituents R² and R³is OH. Typical examples are mono- and/or diglycerides based on caproicacid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid,isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid,stearic acid, isostearic acid, oleic acid, elaidic acid, petroselicacid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid,gadoleic acid, behenic acid and erucic acid and technical mixturesthereof. Technical partial glycerides containing palmitic acid andstearic acid in a ratio by weight of 40:60 to 60:40 are preferably used.Alcohol Polyglycol Ethers

Alcohol polyglycol ethers which form component (b) are products of theaddition of ethylene oxide onto linear fatty alcohols, branchedoxoalcohols or Guerbet alcohols which preferably correspond to formula(II):R⁴O(CH₂CH₂O)_(q)H  (II)in which R⁴ is a linear or branched alkyl and/or alkenyl groupcontaining 6 to 24 and preferably 16 to 18 carbon atoms and q is anumber of 5 to 40 and preferably 10 to 30. Typical examples are theadducts of on average 5 to 40 and preferably 10 to 30 mol ethylene oxidewith caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capricalcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetylalcohol, hexyl decanol, palmitoleyl alcohol, stearyl alcohol, isostearylalcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolylalcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol,gadoleyl alcohol, octyl dodecanol, behenyl alcohol, erucyl alcohol andbrassidyl alcohol and technical mixtures thereof. Mixtures of adducts ofon average 10 to 12 and 15 to 20 mol, respectively, of ethylene oxidewith cetearyl alcohol which are distinguished by a particularhydrophilia profile are particularly preferred. In this case, the ratioby weight between the two components may be, for example, 30:70 to70:30.Fatty Alcohols

The fatty alcohols which form component (c) are primary aliphaticalcohols corresponding to formula (III):

 R⁵OH  (III)

where R⁵ is an aliphatic, linear or branched hydrocarbon radicalcontaining 6 to 24 carbon atoms and 0 and/or 1, 2 or 3 double bonds.Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexylalcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristylalcohol, cetyl alcohol, hexyl decanol, palmitoleyl alcohol, stearylalcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol,petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearylalcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, octyldodecanol, erucyl alcohol and brassidyl alcohol and the technicalmixtures thereof obtained, for example, in the high-pressurehydrogenation of technical methyl esters based on fats and oils oraldehydes from Roelen's oxo synthesis and as monomer fraction in thedimerization of unsaturated fatty alcohols. The alcohol polyglycolethers may have both a conventional broad homolog distribution and anarrow homolog distribution. Preferred fatty alcohols are technicalC₁₂₋₁₈ fatty alcohols such as, for example, coconut oil, cetearyl ortallow fatty alcohol and also behenyl alcohol, the latter significantlyimproving the water resistance of the resulting end products.Wax Esters

Finally, the emulsifiers may contain as another optional component (d)wax esters which preferably correspond to formula (IV):R⁶CO—OR⁷  (IV)where R⁶CO is a linear or branched acyl group containing 6 to 24 andpreferably 16 to 18 carbon atoms and R⁷ is a linear or branched alkylgroup containing 1 to 22 and preferably 16 to 18 carbon atoms, with theproviso that the number of carbon atoms in R⁶CO and R⁷ together is atleast 20 and preferably at least 32. Typical examples are myristylmyristate, myristyl palmitate, myristyl stearate, myristyl isostearate,myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate,cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetylbehenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearylstearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearylerucate, isostearyl myristate, isostearyl palmitate, isostearylstearate, isostearyl isostearate, isostearyl oleate, isostearylbehenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleylstearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleylerucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenylisostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucylmyristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyloleate, erucyl behenate and erucyl erucate.Emulsifier Composition

In one particularly preferred embodiment of the invention, theemulsifiers contain

-   (a) 45 to 60, preferably 50 to 55% by weight partial glycerides,-   (b) 5 to 25, preferably 10 to 20% by weight alcohol polyglycol    ethers,-   (c) 5 to 15, preferably 10 to 12% by weight fatty alcohols and-   (d) 0 to 15, preferably 5 to 10% by weight wax esters,    with the proviso that the quantities shown add up to 100% by weight.    Commercial Applications

The particular effect associated with the emulsifiers according to theinvention is that particularly fine-droplet emulsions which neither gelor crystallize in storage can now also be produced. Accordingly, thepresent invention also relates to their use for the production of PIT ormicroemulsions in which they may be used in quantities of 1 to 15% byweight and preferably in quantities of 5 to 10% by weight, based on thefinal formulations.

Cosmetic and/or Pharmaceutical Preparations

The emulsifiers according to the invention may be used for theproduction of cosmetic and/or pharmaceutical preparations such as, forexample, hair shampoos, hair lotions, foam baths, shower baths, creams,gels, lotions, wax/fat compounds, stick preparations or ointments. Thesepreparations may also contain mild surfactants, oil components,co-emulsifiers, pearlizing waxes, consistency factors, thickeners,superfatting agents, stabilizers, polymers, silicone compounds, fats,waxes, lecithins, phospholipids, biogenic agents, UV protection factors,antioxidants, deodorizers, antiperspirants, antidandruff agents, filmformers, swelling agents, insect repellents, self-tanning agents,tyrosine inhibitors (depigmenting agents), hydrotropes, solubilizers,preservatives, perfume oils, dyes and the like as further auxiliariesand additives.

Surfactants

Suitable surfactants are anionic, nonionic, cationic and/or amphotericor zwitterionic surfactants which are normally present in thepreparations in quantities of about 1 to 70, preferably 5 to 50 and moreparticularly 10 to 30% by weight. Typical examples of anionicsurfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefinsulfonates, alkylether sulfonates, glycerol ether sulfonates, α-methylester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ethersulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide(ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylicacids and salts thereof, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, N-acylamino acids such as, forexample, acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acidcondensates (particularly wheat-based vegetable products) andalkyl—(ether) phosphates. If the anionic surfactants contain polyglycolether chains, they may have a conventional homolog distribution althoughthey preferably have a narrow-range homolog distribution. Typicalexamples of nonionic surfactants are fatty alcohol polyglycol ethers,alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acidamide polyglycol ethers, fatty amine polyglycol ethers, alkoxylatedtriglycerides, mixed ethers and mixed formals, optionally partlyoxidized alk(en)yl oligoglycosides or glucuronic acid derivatives, fattyacid-N-alkyl glucamides, protein hydrolyzates (particularly wheat-basedvegetable products), polyol fatty acid esters, sugar esters, sorbitanesters, polysorbates and amine oxides. If the nonionic surfactantscontain polyglycol ether chains, they may have a conventional homologdistribution, although they preferably have a narrow-range homologdistribution. Typical examples of cationic surfactants are quaternaryammonium compounds, for example dimethyl distearyl ammonium chloride,and esterquats, more particularly quaternized fatty acid trialkanolamineester salts. Typical examples of amphoteric or zwitterionic surfactantsare alkylbetaines, alkylamidobetaines, aminopropionates,aminoglycinates, imidazolinium betaines and sulfobetaines. Thesurfactants mentioned are all known compounds. Information on theirstructure and production can be found in relevant synoptic works, cf.for example J. Falbe (ed.), “Surfactants in Consumer Products”, SpringerVerlag, Berlin, 1987, pages 54 to 124 or J. Falbe (ed.), “Katalysatoren,Tenside und Mineral{hacek over (o)}ladditive (Catalysts, Surfactants andMineral Oil Additives)”, Thieme Verlag, Stuttgart, 1978, pages 123-217.Typical examples of particularly suitable mild, i.e. particularlydermatologically compatible, surfactants are fatty alcohol polyglycolether sulfates, monoglyceride sulfates, mono- and/or dialkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,alkylamidobetaines, amphoacetals and/or protein fatty acid condensates,preferably based on wheat proteins.

Oil Components

Suitable oil components are, for example, Guerbet alcohols based onfatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms,esters of linear C₆₋₂₂ fatty acids with linear C₆₋₂₂ fatty alcohols,esters of branched C₆₋₁₃ carboxylic acids with linear or branched C₆₋₂₂fatty alcohols such as, for example, myristyl myristate, myristylpalmitate, myristyl stearate, myristyl isostearate, myristyl oleate,myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate,cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetylerucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearylisostearate, stearyl oleate, stearyl behenate, stearyl erucate,isostearyl myristate, isostearyl palmitate, isostearyl stearate,isostearyl isostearate, isostearyl oleate, isostearyl behenate,isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate,oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenylmyristate, behenyl palmitate, behenyl stearate, behenyl isostearate,behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate,erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate,erucyl behenate and erucyl erucate. Also suitable are esters of linearC₆₋₂₂ fatty acids with branched alcohols, more particularly 2-ethylhexanol, esters of C₁₈₋₃₈ alkylhydroxycarboxylic acids with linear orbranched C₆₋₂₂ fatty alcohols (cf. DE 197 56 377 A1), more especiallyDioctyl Malate, esters of linear and/or branched fatty acids withpolyhydric alcohols (for example propylene glycol, dimer diol or trimertriol) and/or Guerbet alcohols, triglycerides based on C₆₋₁₀ fattyacids, liquid mono-, di-and triglyceride mixtures based on C₆₋₁₈ fattyacids, esters of C₆₋₂₂ fatty alcohols and/or Guerbet alcohols witharomatic carboxylic acids, more particularly benzoic acid, esters ofC₂₋₁₂ dicarboxylic acids with linear or branched alcohols containing 1to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6hydroxyl groups, vegetable oils, branched primary alcohols, substitutedcyclohexanes, linear and branched C₆₋₂₂ fatty alcohol carbonates suchas, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonatesbased on fatty alcohols containing 6 to 18 and preferably 8 to 10 carbonatoms, esters of benzoic acid with linear and/or branched C₆₋₂₂ alcohols(for example Finsolv® TN), linear or branched, symmetrical ornonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkylgroup such as, for example, Dicaprylyl Ether (Cetiol® OE), ring openingproducts of epoxidized fatty acid esters with polyols, silicone oils(cyclomethicone, silicon methicone types, etc.) and/or aliphatic ornaphthenic hydrocarbons, for example squalane, squalene or dialkylcyclohexanes.

Co-Emulsifiers

Suitable co-emulsifiers are, for example, nonionic surfactants from atleast one of the following groups:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0        to 5 mol propylene oxide onto C₁₂₋₂₂ fatty acids and alkyl        phenols containing 8 to 15 carbon atoms in the alkyl group and        alkylamines containing 8 to 22 carbon atoms in the alkyl group;    -   alkyl and/or alkenyl oligoglycosides containing 8 to 22 carbon        atoms in the alkyl group and ethoxylated analogs thereof;    -   adducts of 1 to 15 mol ethylene oxide with castor oil and/or        hydrogenated castor oil;    -   adducts of 15 to 60 mol ethylene oxide with castor oil and/or        hydrogenated castor oil;    -   partial esters of sorbitan with unsaturated, linear or        saturated, branched fatty acids containing 12 to 22 carbon atoms        and/or hydroxycarboxylic acids containing 3 to 18 carbon atoms        and adducts thereof with 1 to 30 mol ethylene oxide;    -   partial esters of polyglycerol (average degree of        self-condensation 2 to 8), polyethylene glycol (molecular weight        400 to 5000), trimethylolpropane, pentaerythritol, sugar        alcohols (for example sorbitol), alkyl glucosides (for example        methyl glucoside, butyl glucoside, lauryl glucoside) and        polyglucosides (for example cellulose) with saturated and/or        unsaturated, linear or branched fatty acids containing 12 to 22        carbon atoms and/or hydroxycarboxylic acids containing 3 to 18        carbon atoms and adducts thereof with 1 to 30 mol ethylene        oxide;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol according to DE 11 65 574 PS and/or mixed esters        of fatty acids containing 6 to 22 carbon atoms, methyl glucose        and polyols, preferably glycerol or polyglycerol,    -   mono-, di- and trialkyl phosphates and mono-, di- and/or        tri-PEG-alkyl phosphates and salts thereof,    -   wool wax alcohols,    -   polysiloxane/polyalkyl/polyether copolymers and corresponding        derivatives, block copolymers, for example Polyethylene        glycol-30 Dipolyhydroxystearate;    -   polymer emulsifiers, for example Pemulen types (TR-1, TR-2) of        Goodrich;    -   polyalkylene glycols and    -   glycerol carbonate.

The addition products of ethylene oxide and/or propylene oxide withfatty acids, alkylphenols or with castor oil are known commerciallyavailable products. They are homolog mixtures of which the averagedegree of alkoxylation corresponds to the ratio between the quantitiesof ethylene oxide and/or propylene oxide and substrate with which theaddition reaction is carried out. C_(12/18) fatty acid monoesters anddiesters of adducts of ethylene oxide with glycerol are known asrefatting agents for cosmetic formulations from DE 20 24 051 PS.

Alkyl and/or alkenyl oligoglycosides, their production and their use areknown from the prior art. They are produced in particular by reactingglucose or oligosaccharides with primary alcohols containing 8 to 18carbon atoms. So far as the glycoside unit is concerned, bothmonoglycosides in which a cyclic sugar unit is attached to the fattyalcohol by a glycoside bond and oligomeric glycosides with a degree ofoligomerization of preferably up to about 8 are suitable. The degree ofoligomerization is a statistical mean value on which the homologdistribution typical of such technical products is based.

Suitable sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof.Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxideonto the sorbitan esters mentioned are also suitable.

Typical examples of suitable polyglycerol esters are Polyglyceryl-2Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate(Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34),Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate(Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450),Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate(Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane®NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and PolyglycerylPolyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate andmixtures thereof. Examples of other suitable polyolesters are the mono-,di- and triesters of trimethylol propane or pentaerythritol with lauricacid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid,oleic acid, behenic acid and the like optionally reacted with 1 to 30mol ethylene oxide.

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionicsurfactants are surface-active compounds which contain at least onequaternary ammonium group and at least one carboxylate and one sulfonategroup in the molecule. Particularly suitable zwitterionic surfactantsare the so-called betaines, such as the N-alkyl-N,N-dimethyl ammoniumglycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.Finally, cationic surfactants are also suitable emulsifiers, those ofthe esterquat type, preferably methyl-quaternized difatty acidtriethanolamine ester salts, being particularly preferred.

Fats and Waxes

Typical examples of fats are glycerides, i.e. solid or liquid, vegetableor animal products which consist essentially of mixed glycerol esters ofhigher fatty acids. Suitable waxes are inter alia natural waxes such as,for example, candelilla wax, carnauba wax, Japan wax, espartograss wax,cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax,montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax),uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffinwaxes and microwaxes; chemically modified waxes (hard waxes) such as,for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxesand synthetic waxes such as, for example, polyalkylene waxes andpolyethylene glycol waxes. Besides the fats, other suitable additivesare fat-like substances, such as lecithins and phospholipids. Lecithinsare known among experts as glycerophospholipids which are formed fromfatty acids, glycerol, phosphoric acid and choline by esterification.Accordingly, lecithins are also frequently referred to by experts asphosphatidyl cholines (PCs). Examples of natural lecithins are thekephalins which are also known as phosphatidic acids and which arederivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast,phospholipids are generally understood to be mono- and preferablydiesters of phosphoric acid with glycerol (glycerophosphates) which arenormally classed as fats. Sphingosines and sphingolipids are alsosuitable.

Pearlescing Waxes

Suitable pearlescing waxes are, for example, alkylene glycol esters,especially ethylene glycol distearate; fatty acid alkanolamides,especially cocofatty acid diethanolamide; partial glycerides, especiallystearic acid monoglyceride; esters of polybasic, optionallyhydroxysubstituted carboxylic acids with fatty alcohols containing 6 to22 carbon atoms, especially long-chain esters of tartaric acid; fattycompounds, such as for example fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers and fatty carbonates which contain in all atleast 24 carbon atoms, especially laurone and distearylether; fattyacids, such as stearic acid, hydroxystearic acid or behenic acid, ringopening products of olefin epoxides containing 12 to 22 carbon atomswith fatty alcohols containing 12 to 22 carbon atoms and/or polyolscontaining 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixturesthereof.

Consistency Factors and Thickeners

The consistency factors mainly used are fatty alcohols or hydroxyfattyalcohols containing 12 to 22 and preferably 16 to 18 carbon atoms andalso partial glycerides, fatty acids or hydroxyfatty acids. Acombination of these substances with alkyl oligoglucosides and/or fattyacid N-methyl glucamides of the same chain length and/or polyglycerolpoly-12-hydroxystearates is preferably used. Suitable thickeners are,for example, Aerosil® types (hydrophilic silicas), polysaccharides, moreespecially xanthan gum, guar-guar, agar-agar, alginates and tyloses,carboxymethyl cellulose and hydroxyethyl cellulose, also relatively highmolecular weight polyethylene glycol monoesters and diesters of fattyacids, polyacrylates (for example Carbopols® and Pemulen types[Goodrich]; Synthalens® [Sigma]; Keltrol types [Kelco]; Sepigel types[Seppic]; Salcare types [Allied Colloids]), polyacrylamides, polyvinylalcohol and polyvinyl pyrrolidone, surfactants such as, for example,ethoxylated fatty acid glycerides, esters of fatty acids with polyols,for example pentaerythritol or trimethylol propane, narrow-range fattyalcohol ethoxylates or alkyl oligoglucosides and electrolytes, such assodium chloride and ammonium chloride.

Superfatting Agents

Superfatting agents may be selected from such substances as, forexample, lanolin and lecithin and also polyethoxylated or acylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the fatty acidalkanolamides also serving as foam stabilizers.

Stabilizers

Metal salts of fatty acids such as, for example, magnesium, aluminiumand/or zinc stearate or ricinoleate may be used as stabilizers.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives such as, for example, the quaternized hydroxyethyl celluloseobtainable from Amerchol under the name of Polymer JR 400®, cationicstarch, copolymers of diallyl ammonium salts and acrylamides,quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, forexample, Luviquat® (BASF), condensation products of polyglycols andamines, quaternized collagen polypeptides such as, for example,Lauryidimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grünau),quaternized wheat polypeptides, polyethyleneimine, cationic siliconepolymers such as, for example, Amodimethicone, copolymers of adipic acidand dimethylaminohydroxypropyl diethylenetriamine (Cartaretine®,Sandoz), copolymers of acrylic acid with dimethyl diallyl ammoniumchloride (Merquat® 550, Chemviron), polyaminopolyamides as described,for example, in FR 2 252 840 A and crosslinked water-soluble polymersthereof, cationic chitin derivatives such as, for example, quaternizedchitosan, optionally in micro-crystalline distribution, condensationproducts of dihaloalkyls, for example dibromobutane, withbis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationicguar gum such as, for example, Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 ofCelanese, quaternized ammonium salt polymers such as, for example,Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are,for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinylether/maleicanhydride copolymers and esters thereof, uncrosslinked andpolyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammoniumchloride/acrylate copolymers, octylacrylamide/methylmethacrylate/tert.-butylaminoethyl methacrylate/2-hydroxypropylmethacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinylacetate copolymers, vinyl pyrrolidone/dimethylaminoethylmethacrylate/vinyl caprolactam terpolymers and optionally derivatizedcellulose ethers and silicones. Other suitable polymers and thickenerscan be found in Cosm. Toil., 108, 95 (1993).

Silicone Compounds

Suitable silicone compounds are, for example, dimethyl polysiloxanes,methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds which may be both liquid andresin-like at room temperature. Other suitable silicone compounds aresimethicones which are mixtures of dimethicones with an average chainlength of 200 to 300 dimethylsiloxane units and hydrogenated silicates.A detailed overview of suitable volatile silicones can be found in Toddet al. in Cosm. Toil. 91, 27 (1976).

UV protection Factors and Antioxidants

UV protection factors in the context of the invention are, for example,organic substances (light filters) which are liquid or crystalline atroom temperature and which are capable of absorbing ultraviolet orinfrared radiation and of releasing the energy absorbed in the form oflonger-wave radiation, for example heat. UV-B filters can be oil-solubleor water-soluble. The following are examples of oil-soluble substances:

-   -   3-benzylidene camphor or 3-benzylidene norcamphor and        derivatives thereof, for example 3-(4-methylbenzylidene)-camphor        as described in EP 0693471 B1;    -   4-aminobenzoic acid derivatives, preferably        4-(dimethylamino)-benzoic acid-2-ethylhexyl ester,        4-(dimethylamino)-benzoic acid-2-octyl ester and        4-(dimethylamino)-benzoic acid amyl ester;    -   esters of cinnamic acid, preferably 4-methoxycinnamic        acid-2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester,        4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic        acid-2-ethylhexyl ester (Octocrylene);    -   esters of salicylic acid, preferably salicylic acid-2-ethylhexyl        ester, salicylic acid-4-isopropylbenzyl ester, salicylic acid        homomenthyl ester;    -   derivatives of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy4-methoxy4′-methylbenzophenone,        2,2′-dihydroxy-4-methoxybenzophenone;    -   esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic        acid di-2-ethylhexyl ester;    -   triazine derivatives such as, for example,        2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine        and Octyl Triazone as described in EP 0818450 A1 or Dioctyl        Butamido Triazone (Uvasorb® HEB);    -   propane-1,3-diones such as, for example,        1-(4-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione;    -   ketotricyclo(5.2.1.0)decane derivatives as described in EP        0694521 B1.

Suitable water-soluble substances are

-   -   2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline        earth metal, ammonium, alkylammonium, alkanolammonium and        glucammonium salts thereof;    -   sulfonic acid derivatives of benzophenones, preferably        2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts        thereof;    -   sulfonic acid derivatives of 3-benzylidene camphor such as, for        example, 4-(2-oxo-3-bornylidenemethyl)-benzene sulfonic acid and        2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts        thereof.

Typical UV-A filters are, in particular, derivatives of benzoyl methanesuch as, for example,1-(4′-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione,4-tert.butyl-4′-methoxydibenzoyl methane (Parsol 1789) or1-phenyl-3-(4′-isopropylphenyl)-propane-1,3-dione and the enaminecompounds described in DE 197 12 033 A1 (BASF). The UV-A and UV-Bfilters may of course also be used in the form of mixtures. Particularlyfavorable combinations consist of the derivatives of benzoyl methane,for example 4-tert.butyl-4′-methoxydibenzoylmethane (Parsol® 1789) and2-cyano-3,3-phenylcinnamic acid-2-ethyl hexyl ester (Octocrylene) incombination with esters of cinnamic acid, preferably 4-methoxycinnamicacid-2-ethyl hexyl ester and/or 4-methoxycinnamic acid propyl esterand/or 4-methoxycinnamic acid isoamyl ester. Combinations such as theseare advantageously combined with water-soluble filters such as, forexample, 2-phenylbenzimidazole-5-sulfonic acid and alkali metal,alkaline earth metal, ammonium, alkylammonium, alkanolammonium andglucammonium salts thereof.

Besides the soluble substances mentioned, insoluble light-blockingpigments, i.e. finely dispersed metal oxides or salts, may also be usedfor this purpose. Examples of suitable metal oxides are, in particular,zinc oxide and titanium dioxide and also oxides of iron, zirconiumoxide, silicon, manganese, aluminium and cerium and mixtures thereof.Silicates (talcum), barium sulfate and zinc stearate may be used assalts. The oxides and salts are used in the form of the pigments forskin-care and skin-protecting emulsions and decorative cosmetics. Theparticles should have a mean diameter of less than 100 nm, preferablybetween 5 and 50 nm and more preferably between 15 and 30 nm. They maybe spherical in shape although ellipsoidal particles or othernon-spherical particles may also be used. The pigments may also besurface-treated, i.e. hydrophilicized or hydrophobicized. Typicalexamples are coated titanium dioxides, for example Titandioxid T 805(Degussa) and Eusolex® T2000 (Merck). Suitable hydrophobic coatingmaterials are, above all, silicones and, among these, especiallytrialkoxyoctylsilanes or simethicones. So-called micro- or nanopigmentsare preferably used in sun protection products. Micronized zinc oxide ispreferably used. Other suitable UV filters can be found in P. Finkel'sreview in SOFW-Journal 122, 543 (1996) and in Parf. Kosm. 3, 11 (1999).

Besides the two groups of primary sun protection factors mentionedabove, secondary sun protection factors of the antioxidant type may alsobe used. Secondary sun protection factors of the antioxidant typeinterrupt the photochemical reaction chain which is initiated when UVrays penetrate into the skin. Typical examples are amino acids (forexample glycine, histidine, tyrosine, tryptophane) and derivativesthereof, imidazoles (for example urocanic acid) and derivatives thereof,peptides, such as D,L-carnosine, D-carnosine, L-carnosine andderivatives thereof (for example anserine), carotinoids, carotenes (forexample α-carotene, β-carotene, lycopene) and derivatives thereof,chlorogenic acid and derivatives thereof, liponic acid and derivativesthereof (for example dihydroliponic acid), aurothioglucose,propylthiouracil and other thiols (for example thioredoxine,glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl,methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,γ-linoleyl, cholesteryl and glyceryl esters thereof) and their salts,dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionicacid and derivatives thereof (esters, ethers, peptides, lipids,nucleotides, nucleosides and salts) and sulfoximine compounds (forexample butionine sulfoximines, homocysteine sulfoximine, butioninesulfones, penta-, hexa- and hepta-thionine sulfoximine) in very smallcompatible dosages (for example pmole to μmole/kg), also (metal)chelators (for example α-hydroxyfatty acids, palmitic acid, phytic acid,lactoferrine), α-hydroxy acids (for example citric acid, lactic acid,malic acid), humic acid, bile acid, bile extracts, bilirubin,biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acidsand derivatives thereof (for example γ-linolenic acid, linoleic acid,oleic acid), folic acid and derivatives thereof, ubiquinone andubiquinol and derivatives thereof, vitamin C and derivatives thereof(for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (for example vitamin E acetate),vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoateof benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid,nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof,Superoxid-Dismutase, zinc and derivatives thereof (for example ZnO,ZnSO₄), selenium and derivatives thereof (for example seleniummethionine), stilbenes and derivatives thereof (for example stilbeneoxide, trans-stilbene oxide) and derivatives of these active substancessuitable for the purposes of the invention (salts, esters, ethers,sugars, nucleotides, nucleosides, peptides and lipids).

Biogenic Agents

In the context of the invention, biogenic agents are, for example,tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid,retinol, bisabolol, allantoin, phytantriol, panthenol, amino acids,ceramides, pseudoceramides, essential oils, plant extracts and vitamincomplexes.

Deodorants and Germ Inhibitors

Cosmetic deodorants counteract, mask or eliminate body odors. Body odorsare formed through the action of skin bacteria on apocrine perspirationwhich results in the formation of unpleasant-smelling degradationproducts. Accordingly, deodorants contain active principles which act asgerm inhibitors, enzyme inhibitors, odor absorbers or odor maskers.Basically, suitable germ inhibitors are any substances which act againstgram-positive bacteria such as, for example, 4-hydroxybenzoic acid andsalts and esters thereof,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)-urea,2,4,4′-trichloro-2′-hydroxydiphenylether (triclosan),4-chloro-3,5-dimethylphenol,2,2′-methylene-bis-(6-bromo-4-chlorophenol),3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propinyl butyl carbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialperfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil,farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate,glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylicacid-N-alkylamides such as, for example, salicylic acid-n-octyl amide orsalicylic acid-n-decyl amide.

Suitable enzyme inhibitors are, for example, esterase inhibitors.Esterase inhibitors are preferably trialkyl citrates, such as trimethylcitrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and,in particular, triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf,FRG). Esterase inhibitors inhibit enzyme activity and thus reduce odorformation. Other esterase inhibitors are sterol sulfates or phosphatessuch as, for example, lanosterol, cholesterol, campesterol, stigmasteroland sitosterol sulfate or phosphate, dicarboxylic acids and estersthereof, for example glutaric acid, glutaric acid monoethyl ester,glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester,adipic acid diethyl ester, malonic acid and malonic acid diethyl ester,hydroxycarboxylic acids and esters thereof, for example citric acid,malic acid, tartaric acid or tartaric acid diethyl ester, and zincglycinate.

Suitable odor absorbers are substances which are capable of absorbingand largely retaining the odor-forming compounds. They reduce thepartial pressure of the individual components and thus also reduce therate at which they spread. An important requirement in this regard isthat perfumes must remain unimpaired. Odor absorbers are not activeagainst bacteria. They contain, for example, a complex zinc salt ofricinoleic acid or special perfumes of largely neutral odor known to theexpert as “fixateurs” such as, for example, extracts of ladanum orstyrax or certain abietic acid derivatives as their principal component.Odor maskers are perfumes or perfume oils which, besides theirodor-masking function, impart their particular perfume note to thedeodorants. Suitable perfume oils are, for example, mixtures of naturaland synthetic fragrances. Natural fragrances include the extracts ofblossoms, stems and leaves, fruits, fruit peel, roots, woods, herbs andgrasses, needles and branches, resins and balsams. Animal raw materials,for example civet and beaver, may also be used. Typical syntheticperfume compounds are products of the ester, ether, aldehyde, ketone,alcohol and hydrocarbon type. Examples of perfume compounds of the estertype are benzyl acetate, p-tert.butyl cyclohexylacetate, linalylacetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.Ethers include, for example, benzyl ethyl ether while aldehydes include,for example, the linear alkanals containing 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxy-citronellal, lilial and bourgeonal. Examples of suitable ketonesare the ionones and methyl cedryl ketone. Suitable alcohols are anethol,citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethylalcohol and terpineol. The hydrocarbons mainly include the terpenes andbalsams. However, it is preferred to use mixtures of different perfumecompounds which, together, produce an agreeable fragrance. Othersuitable perfume oils are essential oils of relatively low volatilitywhich are mostly used as aroma components. Examples are sage oil,camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil,lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanumoil, ladanum oil and lavendin oil. The following are preferably usedeither individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Antiperspirants reduce perspiration and thus counteract underarm wetnessand body odor by influencing the activity of the eccrine sweat glands.Aqueous or water-free antiperspirant formulations typically contain thefollowing ingredients:

-   -   astringent active principles,    -   oil components,    -   nonionic emulsifiers,    -   co-emulsifiers,    -   consistency factors,    -   auxiliaries in the form of, for example, thickeners or        complexing agents and/or    -   non-aqueous solvents such as, for example, ethanol, propylene        glycol and/or glycerol.

Suitable astringent active principles of antiperspirants are, above all,salts of aluminium, zirconium or zinc. Suitable antihydrotic agents ofthis type are, for example, aluminium chloride, aluminium chlorohydrate,aluminium dichlorohydrate, aluminium sesquichlorohydrate and complexcompounds thereof, for example with 1,2-propylene glycol, aluminiumhydroxyallantoinate, aluminium chloride tartrate, aluminium zirconiumtrichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminiumzirconium pentachlorohydrate and complex compounds thereof, for examplewith amino acids, such as glycine. Oil-soluble and water-solubleauxiliaries typically encountered in antiperspirants may also be presentin relatively small amounts. Oil-soluble auxiliaries such as theseinclude, for example,

-   -   inflammation-inhibiting, skin-protecting or pleasant-smelling        essential oils,    -   synthetic skin-protecting agents and/or    -   oil-soluble perfume oils.

Typical water-soluble additives are, for example, preservatives,water-soluble perfumes, pH regulators, for example buffer mixtures,water-soluble thickeners, for example water-soluble natural or syntheticpolymers such as, for example, xanthan gum, hydroxyethyl cellulose,polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

Film Formers

Standard film formers are, for example, chitosan, microcrystallinechitosan, quaternized chitosan, polyvinyl pyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives, collagen, hyaluronic acid andsalts thereof and similar compounds.

Antidandruff Agents

Suitable antidandruff agents are Pirocton Olamin(1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinonemonoethanolamine salt), Baypival® (Climbazole), Ketoconazol®(4-acetyl-1-{4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}-piperazine,ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfurpolyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate,sulfur tar distillate, salicylic acid (or in combination withhexachlorophene), undecylenic acid, monoethanolamide sulfosuccinate Nasalt, Lamepon® UD (protein/undecylenic acid condensate), zincpyrithione, aluminium pyrithione and magnesium pyrithione/dipyrithionemagnesium sulfate.

Swelling Agents

Suitable swelling agents for aqueous phases are montmorillonites, clayminerals, Pemulen and alkyl-modified Carbopol types (Goodrich). Othersuitable polymers and swelling agents can be found in R. Lochhead'sreview in Cosm. Toil. 108, 95 (1993).

Insect Repellents

Suitable insect repellents are N,N-diethyl-m-toluamide, pentane-1,2-diolor Ethyl Butylacetylaminopropionate.

Self-Tanning Agents and Depigmenting Agents

A suitable self-tanning agent is dihydroxyacetone. Suitable tyrosineinhibitors which prevent the formation of melanin and are used indepigmenting agents are, for example, arbutin, ferulic acid, kojic acid,coumaric acid and ascorbic acid (vitamin C).

Hydrotropes

In addition, hydrotropes, for example ethanol, isopropyl alcohol orpolyols, may be used to improve flow behavior. Suitable polyolspreferably contain 2 to 15 carbon atoms and at least two hydroxylgroups. The polyols may contain other functional groups, more especiallyamino groups, or may be modified with nitrogen. Typical examples are

-   -   glycerol;    -   alkylene glycols such as, for example, ethylene glycol,        diethylene glycol, propylene glycol, butylene glycol, hexylene        glycol and polyethylene glycols with an average molecular weight        of 100 to 1000 dalton;    -   technical oligoglycerol mixtures with a degree of        self-condensation of 1.5 to 10 such as, for example, technical        diglycerol mixtures with a diglycerol content of 40 to 50% by        weight;    -   methylol compounds such as, in particular, trimethylol ethane,        trimethylol propane, trimethylol butane, pentaerythritol and        dipentaerythritol;    -   lower alkyl glucosides, particularly those containing 1 to 8        carbon atoms in the alkyl group, for example methyl and butyl        glucoside;    -   sugar alcohols containing 5 to 12 carbon atoms, for example        sorbitol or mannitol,    -   sugars containing 5 to 12 carbon atoms, for example glucose or        sucrose;    -   amino sugars, for example glucamine;    -   dialcoholamines, such as diethanolamine or        2-aminopropane-1,3-diol.        Preservatives

Suitable preservatives are, for example, phenoxyethanol, formaldehydesolution, parabens, pentanediol or sorbic acid and the other classes ofcompounds listed in Appendix 6, Parts A and B of the Kosmetikverordnung(“Cosmetics Directive”).

Perfume Oils

Suitable perfume oils are mixtures of natural and synthetic fragrances.Natural fragrances include the extracts of blossoms (lily, lavender,rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium,patchouli, petitgrain), fruits (anise, coriander, caraway, juniper),fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery,cardamom, costus, iris, calmus), woods (pinewood, sandalwood, guaiacwood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass,sage, thyme), needles and branches (spruce, fir, pine, dwarf pine),resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum,opoponax). Animal raw materials, for example civet and beaver, may alsobe used. Typical synthetic perfume compounds are products of the ester,ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples ofperfume compounds of the ester type are benzyl acetate, phenoxyethylisobutyrate, p-tert.butyl cyclohexylacetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzylformate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate,styrallyl propionate and benzyl salicylate. Ethers include, for example,benzyl ethyl ether while aldehydes include, for example, the linearalkanals containing 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,lilial and bourgeonal. Examples of suitable ketones are the ionones,α-isomethylionone and methyl cedryl ketone. Suitable alcohols areanethol, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol. The hydrocarbons mainly include theterpenes and balsams. However, it is preferred to use mixtures ofdifferent perfume compounds which, together, produce an agreeablefragrance. Other suitable perfume oils are essential oils of relativelylow volatility which are mostly used as aroma components. Examples aresage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leafoil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, ladanum oil and lavendin oil. The following are preferablyused either individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Dyes

Suitable dyes are any of the substances suitable and approved forcosmetic purposes as listed, for example, in the publication“Kosmetische Färbemittel” of the Farbstoffkommission der DeutschenForschungs-gemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106.These dyes are normally used in concentrations of 0.001 to 0.1% byweight, based on the mixture as a whole.

The total percentage content of auxiliaries and additives may be from 1to 50% by weight and is preferably from 5 to 40% by weight, based on theparticular formulation. The formulations may be produced by standard hotor cold processes and are preferably produced by the phase inversiontemperature method.

EXAMPLES

Various emulsifiers—depending on the composition of the partialglyceride component (a)—were mixed and the resulting mixtures were usedto prepare a PIT emulsion consisting of 70% by weight dicaprylyl ether,10% by weight emulsifier and 20% by weight water. The PIT emulsions werestored for 4 weeks at 40° C. and their phase behavior was visuallyevaluated. (+)=no gelation or crystallization, (o)=slightcrystallization or gelation and (−)=distinct gelation orcrystallization. The results are set out in Table 1. Examples 1 and 2correspond to the invention, Examples C1 to C3 (which correspond tocommercial products) are intended for comparison.

TABLE 1 Gelation and crystallization behavior in storage undertemperature stress (quantities as % by weight) 1 2 C1 C2 C3 Emulsifiercomponent C_(16/18) partial glyceride 50 45 50 45 50 of which % C₁₆ 5045 50 45 30 of which % C₁₈ 50 55 50 55 70 of which % monoglycerides 4040 50 55 50 Ceteareth-10 15 15 15 15 15 Ceteareth-20 10 20 10 20 15Cetearyl alcohol 10 15 10 15 15 Cetyl palmitate 15  5 15  5  5Properties of the PIT emulsion Gelation + + ∘ − − Crystallization + + ∘− −

1. An emulsifier comprising (a) from 45 to 60% by weight of a partial glyceride, (b) from 5 to 25% by weight of an alcohol polyglycol ether, (c) from 5 to 15% by weight fatty alcohol, and (d) from 0 to 15% by weight of a wax ester wherein the monoglycende content of the partial glyceride is less than 50% by weight and wherein the monoglyceride is comprised of palmitic and stearic acid residues in a ratio by weight of from 40:60 to 60:40.
 2. The emulsifier of claim 1 wherein the partial glyceride is a compound of the formula (I):

wherein R¹CO is a linear or branched, saturated and/or unsaturated acyl group having from 6 to 24 carbon atoms, each of R² and R³ is R¹CO or OH and wherein the sum (m+n+p) is from 0 to 100, with the proviso that at least one of R² or R³ is OH.
 3. The emulsifier of claim 1 wherein the alcohol polyglycol ether is a compound of the formula (II):  R⁴O(CH₂CH₂O)_(q)H  (II) wherein R⁴ is a linear or branched alkyl and/or alkenyl group having from 6 to 24 carbon atoms and q is a number from 5 to
 40. 4. The emulsifier of claim 1, wherein the fatty alcohol is a compound of the formula (Ill): R⁵OH  (III) wherein R⁵ is an aliphatic. linear or branched hydrocarbon radical having from 6 to 24 carbon atoms and from 0 to 3 double bonds.
 5. The emulsifier of claim 1 wherein the wax asters corresponding to formula (IV): R⁶CO—OR⁷  (IV) wherein R⁶CO is a linear or branched acyl group having om 6 to 24 carbon atoms and R⁷ is a linear or branched alkyl group having from 1 to 22 carbon atoms, with the proviso that the total number of carbon atoms in R⁶CO and Ris at least
 20. 6. A PIT or microemulsion comprised of an emulsifier of claim
 1. 7. The PIT or microemulsion of claim 6 wherein the amount of the emulsifier of claim 1 is from 1 to 15% by weight. 